Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
  • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment

Definitions

• Inkjet printing has become a popular way of recording images on various media. Some of the reasons include low printer noise, variable content recording, capability of high speed recording, and multi-color recording. These advantages can be obtained at a relatively low price to consumers. As the popularity of inkjet printing increases, the types of use also increase providing demand for new ink compositions.
• Pigmented inks have become particularly popular in recent years due to several advantages over dye-based inks.
• printing pigments can sometimes be a challenge as each pigment has different chemistry and thus, behaves differently when printing using inkjet printing technology.
• some pigments present challenges with respect to stability, decap performance, decel performance, image quality, or the like.
• the formulation of pigment dispersions and/or ink compositions that address some of these and/or other issues can be desirable.
• FIG. 1 schematically represents an example pigment co-dispersed by two dispersants that are associated with the pigment in accordance with the present disclosure
• FIG. 2 depicts an example method of formulating a latex ink composition in accordance with the present disclosure.
• phthalocyanine pigmented ink compositions and thus, the preparation of pigment dispersions and latex ink compositions that include copper phthalocyanine pigments that address some of these challenges can be desirable.
• copper phthalocyanine pigments can sometimes interact with other ink components to produce problems with ink drop velocity deceleration, or“decel.”
• Decel refers to a decrease in the velocity of ink droplets fired from an inkjet printer.
• copper phthalocyanine pigmented inks can be subject to decel after the ink has aged for a period of several months.
• formulating latex ink compositions with copper phthalocyanine pigments poses an additional challenge due to generally high concentrations of solids and other ingredients contained therein.
• Dispersion stability is one issue to consider with such inks, as an unstable dispersion can lead to jettability issues. Consequently, it can be difficult to formulate latex ink compositions, as well as pigment dispersions suitable for preparing latex ink compositions, with copper phthalocyanine pigments that can exhibit good stability and decel performance.
• an aqueous pigment dispersion can include from 40 wt% to 90 wt% water, from 2 wt% to 30 wt% organic co-solvent, from 7.5 wt% to 30 wt% copper phthalocyanine pigment, from 0.5 wt% to 5 wt% styrene-acrylic dispersant, and from 0.5 wt% to 5 wt% hydrophilic polyurethane dispersant having a weight average molecular weight from 10,000 Mw to 30,000 Mw.
• the styrene-acrylic dispersant and the hydrophilic polyurethane dispersant can be present at a weight ratio from 1 :10 to 2:1. In further examples, the styrene-acrylic dispersant and the hydrophilic polyurethane dispersant can be present at a weight ratio from 1 : 10 to 1 : 1 , 1 :2 to 1 :1 , or 1 :2 to 2:1. In another example, the hydrophilic polyurethane dispersant can have a weight average molecular weight from 12,000 Mw to 20,000 Mw.
• the hydrophilic polyurethane dispersant can be a copolymerization product of monomers including 10 wt% to 50 wt% of an aromatic diol, 10 wt% to 40 wt% of an acid-containing diol, and 25 wt% to 75 wt% of a non-aromatic diisocyanate.
• the monomers can include 15 wt% to 40 wt% of the aromatic diol, 15 wt% to 40 wt% of the acid-containing diol, and 25 wt% to 50 wt% of the non-aromatic diisocyanate.
• aromatic diol copolymerized in the hydrophilic polyurethane dispersant can be:
• a latex ink composition can include an aqueous liquid vehicle, from 0.3 wt% to 7 wt% copper phthalocyanine pigment co-dispersed by a styrene-acrylic dispersant and a hydrophilic polyurethane dispersant having a weight average molecular weight from 10,000 Mw to 30,000 Mw, and from 1 wt% to 15 wt% latex particles.
• the styrene-acrylic dispersant and the hydrophilic polyurethane dispersant can be present at a weight ratio from 1 : 10 to 2:1.
• the hydrophilic polyurethane dispersant can be a copolymerization product of monomers including an aromatic diol, an acid-containing diol, and a non-aromatic diisocyanate.
• the monomers of the hydrophilic polyurethane dispersant can be copolymerized in amounts of 10 wt% to 50 wt% of the aromatic diol, 10 wt% to 40 wt% of the acid-containing diol, and 25 wt% to 75 wt% of the non-aromatic diisocyanate.
• the monomers can include 15 wt% to 40 wt% of the aromatic diol, 15 wt% to 40 wt% of the acid-containing diol, and 25 wt% to 50 wt% of the non-aromatic diisocyanate.
• the aromatic diol can be any of compounds (I) through (XI) mentioned above.
• the non-aromatic diisocyanate can be:
• the copper phthalocyanine pigment and the total dispersant content in the latex ink composition can be present at a weight ratio from 15:1 to 2:1.
• the styrene-acrylic dispersant can have a weight average molecular weight ranging from 4,000 Mw to 30,000 Mw and an acid number ranging from 100 mg/g to 350 mg/g
• the hydrophilic polyurethane dispersant can have an acid number from 40 mg/g to 100 mg/g.
• the hydrophilic polyurethane dispersant can have an average particle size ranging from 0.1 nm to 30 nm.
• the latex particles can include a polymerization product of monomers including: a copolymerizable surfactant; an aromatic monomer selected from styrene, an aromatic (meth)acrylate monomer, and an aromatic (meth)acrylamide monomer; and multiple aliphatic (meth)acrylate monomers or multiple aliphatic
• the latex particles can include a polymerization product of a copolymerizable surfactant such as HitenolTM BC-10, BC-30, KH-05, or KH-10.
• the latex particles can include a polymerization product of styrene, methyl methacrylate, butyl acrylate, and methacrylic acid.
• the latex particles can include a first heteropolymer phase and a second heteropolymer phase, wherein the first
• heteropolymer phase is a polymerization product of multiple aliphatic (meth)acrylate monomers or multiple aliphatic (meth)acrylamide monomers.
• the second heteropolymer phase can be a polymerization product of an aromatic monomer with a cycloaliphatic monomer, wherein the aromatic monomer is an aromatic (meth)acrylate monomer or an aromatic (meth)acrylamide monomer, and wherein the cycloaliphatic monomer is a cycloaliphatic (meth)acrylate monomer or a cycloaliphatic
• the second heteropolymer phase can have a higher glass transition temperature than the first heteropolymer phase.
• a method of formulating a latex ink composition can include admixing an aqueous latex dispersion and an aqueous pigment dispersion including a copper phthalocyanine pigment co-dispersed by a styrene-acrylic dispersant and a hydrophilic polyurethane dispersant having a weight average molecular weight from 10,000 Mw to 30,000 Mw in a liquid vehicle to form the latex ink composition.
• the latex ink composition can include from 0.3 wt% to 7 wt% of the copper phthalocyanine pigment and from 1 wt% to 15 wt% latex particles.
• the hydrophilic polyurethane dispersant can be a copolymerization product of monomers including 10 wt% to 50 wt% of an aromatic diol, 10 wt% to 40 wt% of an acid-containing diol, and 25 wt% to 75 wt% of a non-aromatic diisocyanate.
• the monomers can include 15 wt% to 40 wt% of the aromatic diol, 15 wt% to 40 wt% of the acid-containing diol, and 25 wt% to 50 wt% of the non-aromatic diisocyanate.
• aqueous pigment dispersions, latex ink compositions, and method of preparing latex ink compositions presented herein can incorporate copper
• Phthalocyanine is an organic molecule including the general formula C32H I 8 N 8 having the following structure:
• Copper phthalocyanine pigments can be metal complexes in which a copper atom associates with the central nitrogen atoms of the phthalocyanine structure, replacing the two hydrogen atoms of the central NH groups.
• Pigment Blue 15 has the following structure:
• copper phthalocyanine pigments often do not actually include a phthalocyanine molecule itself, but rather are derived from phthalocyanine.
• copper phthalocyanine pigments can include halogen atoms attached to the aromatic rings of the phthalocyanine structure, such as chlorine and brome in particular.
• the copper phthalocyanine pigments used in the pigment dispersions and inks described herein can be a phthalocyanine blue pigment or a phthalocyanine green pigment.
• the copper phthalocyanine pigment can include PB 15:3, PB 15:4, PG 7, PG 36, or a combination thereof.
• the copper phthalocyanine pigment can be present at varying
• the copper phthalocyanine pigment can be present in an aqueous pigment dispersion (used to formulate the ink compositions) at from 7.5 wt% to 30 wt%.
• the copper phthalocyanine pigment can be present in the aqueous pigment dispersion at from 10 wt% to 20 wt%, or from 12 wt% to 18 wt%. These weight percentages are intended to be independent of the two dispersants that are included in the aqueous pigment dispersion as a whole.
• the copper phthalocyanine pigment can be present in an aqueous pigment dispersion (used to formulate the ink compositions) at from 7.5 wt% to 30 wt%.
• the copper phthalocyanine pigment can be present in the aqueous pigment dispersion at from 10 wt% to 20 wt%, or from 12 wt% to 18 wt%.
• phthalocyanine pigment (dispersed by the two dispersants) can be present at from 0.3 wt% to 7 wt%, from 0.4 wt% to 6 wt%, or from 0.5 wt% to 5 wt% in the latex ink composition.
• the pigment in the pigment dispersion can become diluted with additional ingredients, such as additional water or other liquid vehicle compositions, latex, etc.
• the weight ratio of copper phthalocyanine pigment to total dispersant content (e.g., both types of dispersant included) in the aqueous pigment dispersion or the latex ink composition can vary.
• the weight ratio can be from 15:1 to 2:1 , from 10:1 to 2: 1 , from 5:1 to 3: 1 , etc.
• the copper phthalocyanine pigment can be co-dispersed by a styrene-acrylic dispersant and a hydrophilic polyurethane dispersant within these weight ratios, as an example.
• FIG. 1 schematically depicts a copper phthalocyanine pigment 100 that is co-dispersed by two dispersants, namely a styrene-acrylic dispersant 102 and a hydrophilic polyurethane 104 as shown in FIG. 1.
• the weight ratio of styrene-acrylic dispersant to hydrophilic polyurethane dispersant can be from 1 : 10 to 2: 1 , 1 : 10 to 1 : 1 , from 1 :2 to 2:1 , or from 1 :2 to 1 : 1.
• the weight ratio can be about 2:1 , about 1 :1 , or about 1 :2.
• the structure of the pigments and the dispersants is not intended to be to scale or to represent chemical structure, but rather to simply show that there are two different types of dispersants associated with a surface of the copper phthalocyanine pigment.
• the dispersants are not covalently attached to the pigment surface, but rather
• the styrene-acrylic dispersant can associate with the pigment through tt-stacking between the aromatic rings of the copper phthalocyanine pigment and of styrene, adsorption or other similar attractions.
• the hydrophilic polyurethane dispersant can associate with the pigment through adsorption, hydrogen bonding, or other similar attractions.
• the styrene-acrylic dispersant can have a weight average molecular weight from 4,000 Mw to 30,000 Mw. In another example, the styrene-acrylic dispersant can have a weight average molecular weight of 8,000 Mw to 28,000 Mw, from 12,000 Mw to 25,000 Mw, from 15,000 Mw to 25,000 Mw, from 15,000 Mw to 20,000 Mw, or about 17,000 Mw. Regarding the acid number, the styrene-acrylic dispersant can have an acid number from 100 to 350, from 120 to 350, from 150 to 300, from 180 to 250, or about 214, for example.
• Exemplary commercially available styrene- acrylic dispersants can include Joncryl ® 671 , Joncryl ® 71 , Joncryl ® 96, Joncryl ® 680, Joncryl ® 683, Joncryl ® 678, Joncryl ® 690, Joncryl ® 296, Joncryl ® 671 , Joncryl ® 696 or Joncryl ® ECO 675 (all available from BASF Corp., Germany).
• the hydrophilic polyurethane can also be included to provide additional dispersion properties to the copper phthalocyanine pigment.
• the hydrophilic polyurethane can have a weight average molecular weight ranging from 10,000 Mw to 30,000 Mw, or from 12,000 Mw to 20,000 Mw.
• the hydrophilic polyurethane dispersant can have a weight average molecular weight of about 13,000 Mw to 16,000 Mw.
• the hydrophilic polyurethane can have an acid number ranging from 40 to 100, from 40 to 85, from 40 to 75, or from 40 to 60.
• the particle size of the hydrophilic polyurethane dispersant can range from 0.1 nm to 30 nm, from 1 nm to 25 nm, from 10 nm to 30 nm, or from 2 nm to 8 nm.
• the hydrophilic polyurethane dispersant can be a copolymerization product of a non-aromatic diisocyanate, an acid-containing diol, and an aromatic diol, for example.
• the hydrophilic polyurethane dispersant can be a copolymerization product of 10 wt% to 50 wt% of an aromatic diol, 10 wt% to 40 wt% of an acid-containing diol, and 25 wt% to 75 wt% of a non-aromatic
• non-aromatic diisocyanates that can be used can include structures (XII) through (XV) shown above, or a combination thereof.
• the non-aromatic diisocyanate can be isophorone diisocyanate (XII).
• the non-aromatic diisocyanate can be present in the copolymerization reaction from 25 wt% to 75 wt%, from 25 wt% to 65 wt%, or from 25 wt% to 50 wt%.
• the non-aromatic diisocyanate can be an aliphatic or cycloaliphatic diisocyanate.
• Exemplary acid-containing diol monomers that can be used in the copolymerization reaction can include dimethylolpropionic acid, dimethyiol butanoic acid, dihydroxymaleic acid, tartaric acid, or combinations thereof.
• the acid-containing diol can be dimethylolpropionic acid.
• the acid- containing diol can be present in the copolymerization reaction at from 10 wt% to 40 wt%, from 10 wt% to 30 wt%, or from 15 wt% to 25 wt%.
• the aromatic diol can include two or more hydroxyl groups.
• Specific examples of the aromatic diol can include structures (I) through (XI) shown above.
• the aromatic diol can be Bisphenol A ethoxylate (BPAE) (structure (X)).
• the aromatic diol can be present in the copolymerization reaction at from 10 wt% to 50 wt%, from 15 wt% to 40 wt%, or from 20 wt% to 30 wt%.
• the aromatic diol can have a weight average molecular weight from 200 Mw to 2,000 Mw, from 200 Mw to 1 ,000 Mw, or from about 250 Mw to about 600 Mw.
• the copolymerization reaction can further include a polyethyleneoxide compound.
• the polyethyleneoxide compound can include polyetheramines, methoxy polyethylene glycol, polyethyleneoxide diol, or combinations thereof.
• Commercially available examples can include YMERTM N-120 (Perstop Holding AB, Sweden),
• the polyethyleneoxide compound can be present at from 0 wt% to 5 wt%, from 0.9 wt% to 1.2 wt%, or from 0.1 wt% to 1 wt%. In one example, the polyethylene compound can have a water solubility of greater than 10 wt% and a hydroxyl
• the aqueous pigment dispersion and the latex ink composition can further include organic co-solvent.
• the organic co-solvent can be present at from 2 wt% to 30 wt%, from 5 wt% to 25 wt%, from 15 wt% to 30 wt%, or from 5 wt% to 10 wt%.
• more organic co-solvent or less organic co-solvent may be used, e.g., by diluting the organic co-solvent content or by adding more organic co-solvent when formulating the latex ink composition.
• the organic co-solvent in the latex ink composition, can be present at from 5 wt% to 40 wt%, from 10 wt% to 35 wt%, from 15 wt% to 30 wt%, from 20 wt% to 30 wt%, or from 10 wt% to 30 wt%.
• Water can also be included in the aqueous pigment dispersion and in the latex ink composition. The amount of water in the aqueous pigment dispersion from 40 wt% to 90 wt%, from 50 wt% to 85 wt%, or from 60 wt% to 90 wt%.
• the water content in the latex ink composition can be from 20 wt% to 98 wt%, from 30 wt% to 80 wt%, from 40 wt% to 90 wt%, or from 50 wt% to 75 wt%.
• the aqueous pigment dispersion can be used to formulate the latex ink composition of the present disclosure.
• organic co-solvent, copper phthalocyanine pigment, dispersants, other ingredients that may be present in the aqueous pigment dispersion more of these components or these types of components can be admixed with the aqueous pigment dispersion, along with a latex (which includes by definition additional water and latex particulates, and potentially other ingredients), to form a latex ink composition suitable for jetting from inkjet architecture.
• the aqueous pigment dispersion can be formulated in the latex ink composition so that the pigment content can be present at from 0.3 wt% to 7 wt%, from 0.4 wt% to 6 wt%, or from 0.5 wt% to 5 wt% while the pigment to dispersant ratio can be varied from 2 to 10.
• the latex ink compositions of the present disclosure can further include latex particles.
• the latex particles can be present at from 1 wt% to 15 wt%, from 3 wt% to 12 wt%, or from 5 wt% to 10 wt%.
• the latex particles can include a first heteropolymer phase and a second heteropolymer phase.
• the two phases can be physically separated in the latex particles, such as in a core- shell configuration, a two-hemisphere configuration, smaller spheres of one phase distributed in a larger sphere of the other phase, interlocking strands of the two phases, and so on.
• the first heteropolymer phase can be polymerized from two or more aliphatic (meth)acrylate ester monomers or two or more aliphatic (meth)acrylamide monomers.
• the second heteropolymer phase can be polymerized from a cycloaliphatic monomer and an aromatic monomer.
• the cycloaliphatic monomer can be a cycloaliphatic
• the aromatic monomer can be an aromatic (meth)acrylate monomer or an aromatic (meth)acrylamide monomer.
• the second heteropolymer phase can have a higher T g than the first heteropolymer phase.
• the first heteropolymer composition may be considered a soft polymer composition and the second heteropolymers composition may be considered a hard polymer composition
• the first heteropolymer composition can be present in the latex particles in an amount ranging from about 15 wt% to about 70 wt% of a total weight of the polymer particle and the second heteropolymer composition can be present in an amount ranging from about 30 wt% to about 85 wt% of the total weight of the polymer particle.
• the first heteropolymer composition can be present in an amount ranging from about 30 wt% to about 40 wt% of a total weight of the polymer particle and the second heteropolymer composition can be present in an amount ranging from about 60 wt% to about 70 wt% of the total weight of the polymer particle.
• the first heteropolymer composition can be present in an amount of about 35 wt% of a total weight of the polymer particle and the second heteropolymer composition can be present in an amount of about 65 wt% of the total weight of the polymer particle.
• the first heteropolymer phase can include aliphatic (meth)acrylate ester monomers such as linear aliphatic (meth)acrylate ester monomers and/or cycloaliphatic (meth)acrylate ester monomers.
• linear aliphatic (meth)acrylate ester monomers can include ethyl acrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, isooctyl acrylate, isooctyl acrylate, isooctyl
• cycloaliphatic (meth)acrylate ester monomers can include cyclohexyl acrylate, cyclohexyl methacrylate,
• heteropolymer phase can be cyclohexyl acrylate, cyclohexyl methacrylate,
• the aromatic monomer of the second heteropolymer phase can be 2-phenoxyethyl methacrylate, 2- phenoxyethyl acrylate, phenyl propyl methacrylate, phenyl propyl acrylate, benzyl methacrylate, benzyl acrylate, phenylethyl methacrylate, phenylethyl acrylate, benzhydryl methacrylate, benzhydryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- hydroxy-3-phenoxypropyl methacrylate, N-benzyl methacrylamide, N-benzyl acrylamide, N,N-diphenyl methacrylamide, N,N-diphenyl acrylamide, naphthyl methacrylate, naphthyl acrylate, phenyl methacrylate, phenyl acrylate, or a combination thereof.
• the latex particles can be prepared by flowing multiple monomer streams into a reactor.
• An initiator can also be included in the reactor.
• the initiator may be selected from a persulfate, such as a metal persulfate or an ammonium persulfate.
• the initiator may be selected from a sodium persulfate, ammonium persulfate or potassium persulfate.
• the latex particles can have a particle size ranging from 20 nm to 500 nm, from 50 nm to 350 nm, or from 150 nm to 270 nm.
• a latex ink composition can be prepared to include the ingredients in Table 1 below. These ranges are exemplary only, and thus, can be modified.
• the latex ink compositions can further include other liquid or solid components.
• the ink composition can include wax particles.
• the wax particles can be from a naturally occurring wax, a synthetic wax, or a combination thereof.
• Exemplary waxes can include beeswax, lanolin, carnauba, jojoba, paraffin, microcrystalline, micronized, polyethylene, polypropylene, polyamide, poly tetrafluoroethylene, or combinations thereof.
• the wax can be polyethylene emulsion.
• a commercially available example can include AquaslipTM and LiquilubeTM 405 (both available from The Lubrizol Corp., Ohio).
• the wax particles can be filtered.
• the wax particles can be included in the latex ink composition from about 0.1 wt% to about 3 wt%, from about 0.1 wt% to 2 wt%, or from about 0.5 wt% to 1 wt%.
• the organic co- solvent can include 2-methyl-1 ,3-propanediol (MPDiol); 2-pyrrolidone (2P), 1 .2-propanediol, 1 ,2-butanediol, ethylene glycol, 2-methyl-2,4-pentanediol,
• the aqueous liquid vehicle can include organic co-solvents compatible with the various components in the latex ink
• composition including polar solvents such as alcohols, amides, esters, ketones, lactones, and ethers.
• co-solvent can be an aliphatic alcohol, an aromatic alcohol, diol, glycol ether, polyglycol ether, caprolactam, formamide, acetamide, long chain alcohol, or combinations thereof.
• Exemplary co-solvents can include 2-methyl-1 ,3-propanediol (MPDiol); 2-pryollidone (2P); 2-ethyl-2- (hydroxymethyl)-l , 3-propane diol; glycerol; N-methylpyrrolidone; dimethyl sulfoxide; sulfolane; glycol ethers; alkyldiols; 1 ,2-hexanediol; ethoxylated glycerols; LEG-1
• the co-solvent in the aqueous liquid vehicle can include 2-methyl-1 ,3-propanediol; 2-pryollidone; or combinations thereof.
• the co-solvents can be present in the aqueous liquid vehicle, as mentioned, at from 5 wt% to 40 wt%, from 10 wt% to 35 wt%, from 15 wt% to 30 wt%, from 20 wt% to 30 wt%, or from 10 wt% to 30 wt%.
• the aqueous liquid vehicle can include surfactant.
• the surfactant can include a non-ionic surfactants, fluorosurfactants, phosphate ester surfactants, alkyl polyethylene oxides, alkyl phenyl polyethylene oxides, polyethylene oxide block copolymers, acetylenic polyethylene oxide,
• polyethylene oxide amines polyethylene oxide esters, dimethicone copolyols, ethoxylated surfactants, alcohol ethoxylated surfactants, or combinations thereof.
• Exemplary surfactants can include oleth-3 phosphate (commercially available as CrodafosTM N3 acid from Croda ® International Pic, England); secondary alcohol ethoxylates (commercially available as Tergitol ® 15-S-7 and Tergitol ® TM-6from Union Carbide Corp., New York); fluorinated polymeric surfactant (commercially available as CapstoneTM FS-35 available from DuPontTM Chemicals and Fluoroproducts, Delaware); or combinations thereof. If present, the surfactant can be included in the aqueous liquid vehicle from 0.1 wt% to 5 wt%, from 1 wt% to 3 wt%, or from 0.5 wt% to 2.5 wt%.
• oleth-3 phosphate commercially available as CrodafosTM N3 acid from Croda ® International Pic, England
• secondary alcohol ethoxylates commercially available as Tergitol ® 15-S-7 and Tergitol ® TM
• the aqueous liquid vehicle can include various other additives.
• additives can include additives to inhibit the growth of harmful microorganisms, sequestering agents, viscosity modifiers, and the like.
• Exemplary additives that can be used to inhibit the growth of harmful microorganisms can include biocides, fungicides, microbial agents, and the like.
• Commercially available microbial agents can include Acticide ® (Thor Specialties, Inc., Connecticut), NuoseptTM (AshlandTM Global Holdings Inc., North America), UcarcideTM (Union carbide Corp., New Jersey), Vancide ® (R.T. Vanderbilt Holding Co., Connecticut), ProxelTM (Imperial Chemical Industries, Inc., New Jersey), or combinations thereof.
• Sequestering agents such as EDTA (ethylene diamine tetra acetic acid)
• EDTA ethylene diamine tetra acetic acid
• buffer solutions can be used to control the pH of the ink.
• Viscosity modifiers and buffers can also be present, as well as other additives to modify properties of the latex ink compositions as desired.
• the latex ink compositions presented herein can exhibit good stability when stored as a bulk dispersion. These latex ink compositions do not exhibit significant changes in viscosity following exposure to even multiple freeze-thaw cycles (a single freeze-thaw cycle includes freezing the latex ink composition to -40 °C and then heating to 70 °C), and furthermore, they do not tend to exhibit significant changes in viscosity following accelerated shelf-life testing.
• the latex ink compositions described herein can exhibit good decal performance, even after Accelerated Shelf Life (ASL) test.
• Decel refers to the decrease of drop velocity over time during continuous firing of the pen. No decel is preferred, or in other words, the preferred decrease of drop velocity is 0.
• Acceptable decel performance for the inks can be characterized by the decrease of drop velocity less than 1 m/s. Without being limited by theory, it is believed that these features can be attributed to the co-dispersion of the copper phthalocyanine pigments by the styrene-acrylic dispersant and the hydrophilic polyurethane dispersant.
• the present disclosure is also drawn to a method for formulating a latex ink composition, as shown in FIG. 2.
• the method 200 can include admixing 202 an aqueous latex dispersion and an aqueous pigment dispersion in a liquid vehicle to form the latex ink composition.
• the aqueous pigment dispersion can be a copper phthalocyanine pigment co-dispersed by a styrene-acrylic dispersant and a hydrophilic polyurethane dispersant.
• the hydrophilic polyurethane dispersant can have a weight average molecular weight from 10,000 Mw to 30,000 Mw.
• the latex ink composition can include from 0.3 wt% to 7 wt% of the copper phthalocyanine pigment and from 1 wt% to 15 wt% latex particles.
• the individual components of the latex ink composition can be as described herein.
• the term“about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be“a little above” or“a little below” the endpoint.
• the degree of flexibility of this term can be dictated by the particular variable and would be within the knowledge of those skilled in the art to determine based on experience and the associated description herein.
• Decel is short for deceleration and refers to a decrease of drop velocity in the unit meters per second (m/s) over time during continuous firing of a print head.
• Volume-weighted mean diameter is the mean diameter of a co-dispersed copper phthalocyanine pigment particles within a specific volume.
• the term“acid value or“acid number” refers to the minimum mass of potassium hydroxide (KOH) in milligrams that can be used to neutralize one gram of substance, such as the various dispersants disclosed herein.
• a weight ratio range of about 1 wt% to about 20 wt% should be interpreted to include not only the explicitly recited limits of about 1 wt% and about 20 wt%, but also to include individual weights such as 2 wt%, 11 wt%, 14 wt%, and sub-ranges such as 10 wt% to 20 wt%, 5 wt% to 15 wt%, etc.
• a polyurethane dispersant was prepared from isophorone diisocyanate (IPDI), Bisphenol A ethoxylate (BPAE), 2,2'-dimethylol propionic acid (DMPA), and YmerTM N120 (Perstop), using the relative weight percentages shown below in Table 2, as follows:
• the polyurethane dispersant had a weight average molecular weight of 15,000 Mw.
• the aqueous pigment dispersions included 15 wt% Pigment Blue 15:3, 15 wt% of 2-pyrrolidone, and amounts of Joncryl® 671 (a styrene- acrylic dispersant) and the polyurethane dispersion of Example 1 as shown in Table 3 below. The balance of each dispersion is water.
• Latex particles were formed with two different streams of monomers.
• One monomer stream included a solution of soft component monomers (i.e. , monomers suitable for forming the first heteropolymer composition disclosed herein), and the other monomer stream included an emulsion of several hard and/or hydrophobic component monomers and an additional monomer (i.e. , monomers suitable for forming the second heteropolymer composition disclosed herein).
• the latex particles were prepared as follows. Deionized water (58.6g) was heated to 77°C with mechanical agitation in a reactor. At 77°C, latex seed (5.0g at 49% solids; 67nm particle size) was added to the reactor. Also at 77°C, potassium persulfate (0.2g) dissolved in water (4% solution) was added.
• Feed (D) included an aqueous emulsion of water (30g), copolymerizable surfactant (HITENOL® AR-1025) (7.0g), cyclohexyl methacrylate (45.1 g), cyclohexyl acrylate (6.5g), phenoxyethyl methacrylate (9.1 g), and methacrylic acid (2.6g).
• HITENOL® AR-1025 copolymerizable surfactant
• the resulting polymer particles included a two heteropolymer phases - one of methyl methacrylate, butyl acrylate, and methacrylic acid and the other of cyclohexyl methacrylate, cyclohexyl acrylate, phenoxyethyl methacrylate, and methacrylic acid.
• the example polymer particles were present in an emulsion (i.e., a latex emulsion), and made up 42.4% solids by total weight of the latex emulsion.
• the particle size of the example polymer particles was 0.215 pm (particle size determined using Microtrac Nanotrac Wave II), and the viscosity (at 25°C) of the latex emulsion was less than 50 cps.
• Example 3 The pigment dispersions of Example 2 (Table 3) were then admixed with other ingredients to form latex ink compositions to test ink stability and decel
• each of the aqueous pigment dispersions of Example 2 to provide 2 wt% pigment.
• CrodafosTM is available from Croda ® International Pic.
• Tergitol ® is available from Union Carbide Corp.
• CapstoneTM is available from DuPontTM Chemicals and Fluoroproducts.
• a sample was placed in an oven with the temperature ramped from initial temperature to 70 °C in 20 min, and maintained at 70 °C for 4 hours, decreased from 70 °C to - 40 °C in 20 min and maintained at - 40 °C for 4 hr. This process was repeated, such that each sample was subjected to a total of 5 freeze-thaw cycles.
• each of the samples was allowed to equilibrate to room temperature, and the viscosity and particle size were tested.
• Tables 5A and 5B show the results of testing the pigment dispersions for volume averaged particle size and d95 particle size after freeze-thaw cycles and accelerated shelf life aging.
• T-cycle 5 Freeze-Thaw Cycles from -40 °C to 70 °C
• ASL Accelerated Shelf Life (ASL) at 60 °C
• Mv Volume Averaged Particle Size
• D95 95 Percentile Particle Size.
• the inks were tested for freeze-thaw related changes and accelerated shelf life changes in viscosity and particle size including Mv and D95. The results are shown in Tables 6A-6C.
• the Comparative Ink was prepared from the Comparative Dispersion of Example 2. Inks 1 -3 were prepared with Dispersions 1-3 from Example 2, respectively.
• V Viscosity
• T-cycle 5 Freeze-Thaw Cycles from -40 °C to 70 °C
• ASL Accelerated Shelf Life (ASL) at 60 °C for 1 week
• Mv Volume Averaged Particle Size
• D95 95 Percentile Particle Size.
• Example 4 The ink compositions of Example 4 were also tested for decel
• each of the formulations were filled into a thermal inkjet print head and the drop velocity vs. firing time over 6 seconds was collected. The inks were tested as initially prepared and also after aging for 2 weeks ASL. The loss in velocity is also shown in Table 7 below.
• the comparative ink showed the greatest amount of decel after 2 weeks ASL.
• the comparative ink did not contain the hydrophilic polyurethane dispersant.
• Inks 1 -3 had better decel performance.
• the ratio of the styrene-acrylic dispersant to the polyurethane dispersant was 2:1.
• In ink 2 the ratio was 1 :1 and in ink 3, the ratio was 1 :2.
• the decel results suggest that increasing the amount of hydrophilic polyurethane dispersant relative to the styrene- acrylic dispersant tends to improve the decel performance.
• Inks 2 and 3 had the best decel performance.

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